GENERAL I ARTICLE

Chemical Oscillations
1. Basic Principles and Examples

Monika Sharma and Pra'Veen Kumar

A chemical reaction is usually thought of as coming to-

gether of reactant molecules to form products. The concen-
trations of initial components (reactants) decrease, and
concentrations of products increase until they reach a well
defined state: the equilibrium. This process is accompa-
nied by a decrease of the system free energy (compared at
constant pressure and temperature), until it reaches a mini- Monika Shanna is a JRF
mum in the equilibrium. Thus, it follows from the nature of at the Protein Science and
the law ofmass-action that every simple reaction approaches Engineering Unit,
Institute of Microbial
its equilibrium asymptotically, and the evolution of any
Technology (IMTECH),
physico-chemical system leads invariably to the steady Chandigarh.
state of maximum disorder in the universe. Normally, chemi-
cal systems approach equilibrium in a smooth, frequently
exponential relaxation. Under special circumstances, how-
ever, coherent behavior such as sustained oscillations are
observed and the oscillations of chemical origin have been
present as long as life itseH. Such reactions can be studied
Praveen Kumar is
using mathematical models, the Lotka-Volterra model be- pursuing his PhD in
ing the earliest and the simplest one. chemical dynamics at
Panjab University,
1. Introduction Chandigarh.

Every living system contains hundreds of chemical oscillators.

Some examples are systems such as circadian clocks and rhyth-
mic activity of central nervous system, and other biochemical
processes at the cellular level like the glycolytic pathway, peroxi-
dase-catalysed reaction or the biosynthesis of certain proteins. A
systematic study of oscillating chemical reactions is of consider- Keywords
Chemical oscillations, autoca-
able interest, since these oscillating reactions can be used as
talYSis, Lotka-Volterra model,
prototype examples of the behaviours possible in reactions gov- bistability, hysteresis, Briggs-
erned by non-linear dynamic laws that appear in chemistry, Rauscher reaction .

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RESONANCE I February 2006 43
 GENERAL I ARTICLE

The phenomenological geology, biology and engineering. An understanding of oscilla-

kinetics of oscillating tory processes at molecular level is of great importance, as it
chemical reactions holds the key to the mystery of complex phenomena like sleep
shows that the induction in animals or migratory behaviour of birds, etc.
concentrations of
The phenomenological kinetics of oscillating chemical reac-
reactants, intermedia-
tes and products can
tions shows that the concentrations of reactants, intermediates
and products can vary periodically either in space, e.g., morpho-
vary periodically either
genesis, or in time, e.g., circadian rhythms. It may seem that an
in space, e.g.,
oscillating reaction would require the free energy of the system
morphogenesis, or in
to oscillate as the reactants were converted to products and then
time, e.g., circadian
back to reactants, thus contradicting the Second Law of Ther-
rhythms.
modynamics. In fact, this behaviour is driven by the Gibbs-free-
energy decrease of an overall chemical reaction occurring far
from thermodynamic equilibrium. Such oscillating systems cor-
respond to thermodynamically open systems. A biological cell is
also an open system that can take in nutrients and excrete waste
products of enzyme-catalysed reactions. These reactions are
complex and take place via a number of elementary steps, most
of which involve nonlinear kinetics. Long-lasting chemical os-
cillations can occur only if a proper feedback mechanism is
present. This can be achieved by supplying reactants and
removing products continuously from the reaction vessel.

In this article, we illustrate the interesting features of this now

well studied area of complexity. We discuss autocatalysis,
bistability and provide a recipe for observing oscillations in the
laboratory.

Autocatalysis

Another important feature of most chemical systems that ex-

hibit oscillations is autocatalysis, which is a way to provide
positive feedback to an oscillatory reaction, i.e., the progress of
the reaction is favoured by the product formed. Autocatalysis is
the phenomenon of catalysis of reactions by products formed
during a reaction.

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 GENERAL I ARTICLE

The simplest example of autocatalysis is the reaction: The presence of

A+X ~ 2X (Equivalent to A ~ X) one or more
autocatalytic steps
whose rate law is -d[A]/dt = k[A][X].
in a complex
The presence of one or more autocatalytic steps in a complex chemical
chemical mechanism leads to chemical oscillations. However, as mechanism leads to
the product concentration keeps building, autocatalysis can lead chemical
to explosion, so an inhibition step is also necessary. When oscillations.
autocatalysis and inhibition appear at the same time, the steady
state can be stabilized, where the net rate of increase of all
relevant species is zero. So, oscillations can appear only if the
inhibition step is somehow delayed.

Example of an Autocatalytic Reaction

An example of autocatalysis is provided by Belousov-Zha-

bontinskii reaction (BZ reaction) (Box 1), the first oscillating
reaction to be reported and studied systematically. This is also
the first chemical reactions found to exhibit spatial and tempo-
ral oscillations, i.e., oscillations in time and space, respectively,
even in a small beaker or in a Petri dish. The reaction solution
spreads out as a thin film with a few millimeters thickness in a
Petri dish and after a certain time, blue oxidation fronts propa-
gating on a red background (reduced ferroin; see Box 1) develop
(Figure 1).

Bistability and Hysteresis

Normally, only a single (monos table) steady state is expected for Figure 1. From left to right:
a particular set of reactant concentrations. However, equilib- Propagating oxidation
waves in unstirred layer of
the terroin-malonic acid BZ
reaction. When the wave is
broken at a certain point, a
pairofspiral waves develop
at this point.
Courtesy: Peter Ruoff.
Source: www.ux.his.no/-ruoff/
BZ_Phenomenology. html

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RESONANCE I February 2006 45
 GENERAL I ARTICLE

Box 1. BZ Reaction

In a classical form, BZ reaction is a case of oscillatory chemical reaction in homogeneous solution.

Generally, it consists of oxidation of analogs of an organic acid (commonly malonic acid), by bromate ion
in form ofNaBr03 or KBr03 acidified by sulfuric or nitric acid. As catalyst, mostly Ce(III)/Ce(lV) salts,
Mn(lI) salts and ferroin are used.

The two pictures on the left (Figure A) and right (Figure B) show the BZ reaction with malonic acid as
a substrate in a stirred beaker with ferroin as a catalyst. Oxidized ferro in has a
blue colour and reduced ferro in is red. The solution shows periodic colour
changes due to the alternations between the oxidized state (Figure A) and
reduced state (Figure B). The time period ofBZ systems ranges from a fraction
of a minute up to many minutes depending on the amounts of mineral acid,
organic compound, catalyst, bromate ion and temperature.

The simplest description of the reaction is in terms of two elementary steps:

BrO)- l(aq.) + HBrOiaq.) + H+ (aq.) ~ 2 Br02e(aq.) + H 20 (I)

2 Br0 2e(aq.) + Ce(III)(aq.)+ H+(aq.) ~ 2HBr0 2(aq.) + 2Ce(IV)(aq.)

The product HBr02 is reactant in the first step and provides a feedback
mechan ism that enhances the rate of formation of HBr02 .

Figure A (top). Oxidized ferroin system.

Figure B (bottom). Reduced ferroin system.
Courtesy: Peter Ruoff
Source: www.ux.his.nol-ruoffIBZ_Phenomeno-logy.html

rium systems operating far from equilibrium (autocatalytic reac-

Bistability has an
analogy in electronic
circuitry, such as in
bistable multivibrators,
flip-flop, etc., where
induction of bistable
circuit to make an
abrupt transition from
one state to the other
by means of external
excitation is well
known.
tions) can exhibit a number of steady states, say three or more.
The simplest of these is the existence of a system in two equally
likely (but different) stable states - bistability, a situation arising
out of three steady states, of which two may be stable locally and
experimentally observable, and the third is always unstable.
This bistability has an analogy in electronic circuitry, such as in
bistable multivibrators, flip-flop, etc., where induction of bistable
circuit to make an abrupt transition from one state to the other
by means of external excitation is well known. It can be used for
performance of many digital operations, such as counting and
storing of binary information.

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 GENERAL I ARTICLE

Bistability occurs over a range of values of a suitable IVI

control parameter. This means that the existence of
the system in either of the steady states is decided by a
limited range of values of the parameter. Variation in
the value of such an experimental parameter can possi-
bly move the system between the steady states. Per-
B
turbing the system from the bistability range will
effect the transition of the system to one or the other of
the steady states. This behaviour is described by curves
1\1
obtained in the [X]-[Y] plot (Figure 2). The upper and
lower curves SSII and SSI are the set of stable steady
states for different values of [X], obtained far from equilibrium. Figure 2. System showing
The concentrations [X] represent the reactant supplied to the bistability.
reactor and [Y] represent the concentrations of the product
removed from the reactor, continuously.

Moving along a curve for one steady state, say the lower one, if
the system is brought to the range of values of [X] for which
bistability exists (from SSII to SSI in Figure 2), it will remain in
that state until the limiting value of [X] for this state is reached.
Thus, to effect a transition in one direction, we must pass
beyond the range of parameters for bistability. If we follow the
curve for the other steady state in the reverse direction, we reach
a different limit of the value of [X], at which the reverse transi-
tion takes place, indicating that the system retains memory of Figure 3. When an interme-
the direction of the bistability region it left or re-entered. This diate Z is added to reactor
systemX-Y.
peculiar behaviour is called hysteresis and has its analogy in
magnetism, where the retention of magnetism by the
iron sample, leads to the complete cycle of magneti- lYJ
sation and demagnetisation in the form of a loop.

When we introduce an intermediate Z to the reactor,

which reacts with both X and Y, to produce Y and X,
respectively, we observe that the system switches peri-
odically between the upper and the lower curves
(Figure 3), giving rise to oscillations. This added inter-
mediate must show two features: the rates of reactions of
the intermediate with one or more species present in the IX\

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 GENERAL I ARTICLE

Box 2. Recipe for Briggs-Rauscher Reaction

Solution I: [H 2 S0 4 ] 0.0265M + [MnS0 4 ] 0.0067M + [Malonic acid] 0.0500M

Solution II: [KI0 3 ] 0.0670M + [Starch] 0.0300M
Solution III: [H 20 2] 30% solution

initial bistable system on the two steady state branches must

differ to a considerable extent; and its reactions with the bistable
system must be slower than the reactions of the constituents of
the system with each other. The oscillation is seen as the peri-
odic depletion of the reactants and surge of products. The
existence ofbistability is an interesting aspect in the occurrence
of oscillations.

This is illustrated by the Briggs-Rauscher (BR) [1] reaction

(Box 2), a variant of the BZ reaction. When we mix the three
solutions given in the recipe (see Box 2) and the mixture is
stirred vigorously with a magnetic stirrer, the initial colourless
solution turns amber immediately. Then it turns blue-black,
which fades out to colourless, which again changes to amber.
The colour of the solution thus oscillates between the colourless,
amber, and blue black for some time. The main feedback specie
recognized in this reaction is malonic acid and, bistability is
generated from an autocatalytic decomposition of HzOz by 103'
Upon initial mixing of the solutions, 103- reacts with HzOz to
give HIO z' This step is autocatalytic, assumed to result from a
radical mechanism activated by the presence of Mn2+ ions.

The oscillation is H+ + 103 + HIO z ( ) 210 z + Hz0(l)

seen as the periodic
10z + Mnz+ + HzO ~ HIO z + [MnOH]2+ (2)
depletion of the [MnOH]2+ eventually generates oxygen
reactants and surge
of products. The [MnOH]2+ + H Z02 ~ Mn2+ + HOO· + H 20 (3)
existence of 2HOO· ~ 02 + H 20 2 (4)
bistability is an
This autocatalytic production of HIO z is finally limited by
interesting aspect in
the occurrence of 2HI02 ~ 103 + HOI + H+ (5)
oscillations. H 20 2 + HOI ~ 1- + H+ + 02 + H 20 (6)

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48 RESONANCE I February 2006
 GENERAL I ARTICLE

The HOI produced in equations (5), (6) and (10) reacts with 1- The switching of
producing I z reaction between
the radical and
H+ + HIO z + 1- ~ 2HOI (7)
non-radical modes
HOI + 1- + H+ ~ I z + HzO (8)
is dictated by the
The I z reacts slowly with malonic acid [1-], i.e., whether
the [HI0 2] finds
MA + I z ~ IMA + 1- + H+ (9) enough [1-] to react
2H+ + 103 + 1- ~ HIO z + HOI (10) through nonradical
mode, or gets
This shows that BR reaction involves two stoichiometric radical
involved in the
and non-radical reduction processes. These reactions give rise to
radical autocatalyic
bistability under appropriate flow conditions. The non-radical
step.
sequence (equations 7-10) lowers the concentrations of I z and
1-, denoted by [Iz] and [1-], respectively. This makes the system
undergo a switchover to the radical sequence (equations 1-4).
The decreased [1-] and increased [HIO z] (equations 1-2), result
in increase of [HOI] by radical reactions to such an extent that
Equation 6 begins and [1-] increases. The presence of amber
colour corresponds to the concentrations of HOI greater than 1-
concentrations. The increase in [1-] switches the system to non-
radical mode, thereby increasing [12] (by equation 8). The blue-
black colour is present when [1-] is greater than [HOI] due to the
formation of a blue starch-iodide complex. [12] reaches a maxi-
mum and begins to fall with [1-] still rising as [12] continues to
drop until the solution finally fades out. When [1-] reaches a
critical level, [HIOz] falls suddenly, increasing [1-], switching
the system back to the non-radical path, and the cycle is again
allowed to repeat. Thus, the switching of reaction between the
radical and non-radical modes is dictated by the [1-], i.e., whether
the [HIO z] finds enough [1-] to react through nonradical mode,
or gets involved in the radical autocatalyic step.

The Briggs-Rauscher reaction, like the BZ reaction, has been

studied extensively. In experiments using the continuous-flow,
stirred-tank reactor (CSTR)Z, the complex oscillations as well as
the bistability involved in the BR reaction have been seen. The
bistability observed can also be explained by the phase diagram

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 GENERAL I ARTICLE

(Figure 2 with [X] and [V] as input-flow concentration [I 2]0 and

steady state iodine concentration [12]ss' respectively). Curves
SSII and SSI denote steady state II and steady state I, respec-
tively. The steady state [l2]SS can either be higher or lower than
[1 2]0' depending upon the branch of hysteresis attained. At low
input flow, system attains SSII where [12JsSII > [1 2]0' On the other
hand, at high input flow, the system reaches SSI where [1 2]sSI <
[1 2]0' Under some conditions, a curious phenomenon is ob-
served, known as inverse regulationz of [I2]' where it is seen that
increasing [Iz]o beyond its critical value results in a drop in [12] in
the reactor, and the reverse is observed when [12]0 is decreased
below the critical value.

Concluding Remarks

The BR oscillator studied above is one of the most spectacular

elementary chemical oscillators. It can be used for the purpose of
lecture demonstrations, and it appears like a magic show! There
are many other kinds of oscillating systems known and studied
at present. All of these have underlying plans of evolution; they
all have autocatalytic components. Often the reaction is carried
out in a continuous-flow reactor; the conditions are varied to
find the bistability region; and another substance exerting sig-
Address for Correspondence nificant by different effects on the two branches of steady states
Monika Sharma of system may be added to the original oscillatory system. In
Protein Science and
Part II of this article, we describe a very simple mathematical
Engineering Unit
Institute of Microbial
model, the prey-predator model, of an oscillatory chemical reac-
Technology tion. We carry out detailed analysis of this model and show a few
Sector 39A results.
Chandigarh 160 036
Email:mondyn@gmail.com Suggested Reading

Praveen Kumar
Department of Chemistry
and Centre for Advanced
Studies in Chemistry
Punjab Univesity
Chandigarh 160014. India.
Email:chemdyn@pu.ac.in
[1] T C Briggs and W C Rauscher, J. Chem. Edu., Vol.50, p.496, 1973.
[2] R M Noyes and S Furrow, J. Am. Chem. Soc., Vol.104, pp. 45-48, 1982.
[3] P De Kepper and I R Epstein, J. Am. Chem. Soc., Vol.104, pp. 49-55,
1982.
[41 I REpstein, KKustin,PDeKepper and MOrban, Sci.Am., Vol. 248,
No.3,pp.112-1231983.
[5] S K Scott, Oscillations, waves and chaos in chemical kinetics, Oxford
Chemistry Primer #18, Oxford University Press, Oxford, 1994.

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